Azo dyes containing a halomethylbenzoylamino radical



United States Patent Office 3,1175%? Patented Jan. 14, 1964 3,117,962 AZO DYES CONTAINING A HALOMETHYLBEN- ZOYLAMINO RADICAL Werner Rohland and Walter Mesch, Ludwigshafen (Rhine), and Dieter Ludsteck, Ludwigshafen (Rhine), Gartenstadt, and Wilhelm Federkiel, Frankenthal, Pfalz, Germany, assignors to Badische Anilin- & Soda- Fabrik Aktiengesellschaft, Ludwigshafeu (Rhine), Germany No Drawing. Filed Aug. 16, 1960, Ser. No. 49,839 Claims priority, application Germany Aug. 20, 1959 6 Claims. (Cl. 260-162) This invention relates to new azo dyes, a process for the preparation of the same, and the use of the same for dyeing wool, silk, synthetic linear polyamides and cellulose.

It is an object of this invention to provide new azo dyes which will dye textile materials of wool, silk, synthetic linear polyamides and especially cellulose in shades fast to washing. Textile materials include fibers, flock, threads, woven and non-woven textiles. As linear synthetic polyamides there may be specified nylon 6, nylon 66 and nylon 11. The term cellulose includes native cellulose, as for example cotton, and regenerated cellulose, as for example rayon and rayon staple.

Another object of this invention is to provide a process for the production of these new dyes.

The new dyes have the general formula:

III

in which R represents a hydrogen atom, a methyl, methoxy, ethoxy, nitro, sulfonic acid or sulfonic acid amide radical, R represents a hydrogen atom, a sulfonic acid or sulfonic acid amide radical, R represents a hydrogen or chlorine atom or a methyl, methoxy, ethoxy, nitro, acetylamino, benzoylamino, sulfonic acid, sulfonic acid amide, benezeneazo or 4-sulfobenzeneazo radical, R represents a hydrogen or chlorine atom or a methoxy, sulfonic acid or sulfonic acid diethylamide radical, W represents a sulfonic acid radical in 4-, 6- or 7-position to the azo group and R represents a hydrogen atom or a sulfonic acid radical, B represents one of the radicals of the formulae:

I CH2-CH2OH in which Z represents a methyl or beta-hydroxyethyl radical, Z a hydrogen or chlorine atom or a methyl radical, Z, a hydroxy, Z-hydroxyethylamino or amino radical, Z a hydrogen atom or a sultonic acid, carboxylic acid anilide or carboxylic acid-(beta-hydroxyethyl)-amide radical, Z a hydrogen atom or a sulfonic acid radical, Z a hydrogen atom or a sulfonic acid radical, Z a hydrogen atom or a hydroxy radical, Z, a hydrogen atom or a hydroxy or sulfonic acid radical, Z a hydroxy or amino radical, Z a hydrogen atom, a hydroxy, amino, acetylamino, sulfonic acid or benzoylamino radical, Z a hydrogen atom or an amino radical, Z a hydrogen atom or a sulfonic acid radical, Z a hydrogen atom or a sul fonic acid radical, Z a hydrogen atom or a sulfonic acid radical, Z a hydrogen atom or a sulfonic acid radical, Z a methyl or carboxylic acid amide radical, Z a hydroxy or amino radical, Z a hydrogen or chlorine atom or a methyl radical, Z a hydrogen atom, a chlorine atom, a nitro radical, an amino radical or a sulfonic acid radical, Z a hydrogen atom or a sulfonic acid radical and Z a hydrogen or chlorine atom, X represents a chlorine or bromine atom and Y represents a -CO or SO group, and the radical:

-NH-Y CHaX stands instead of the said substituents R Z Z Z Z or Z These new dyes may be prepared in various ways. Thus for example an azo dye of the general formula:

may be reacted with a carboxylic or sulfonic acid halide of the general formula:

CH2X In A, B, X and Y having the meanings given above. This reaction is carried out in aqueous solution or suspension, in organic diluents, for example methanol, ethanol, acetone,

or in mixtures of water and one or more of the said organic diluents, at room temperature or elevated temperature, for example 30 to 100 C., andfpreferably in the presence of an acid-binding substance. Acid-binding substances include sodium or potassium hydroxide, carbonate, bicarbonate or acetate, calcium or magnesium oxide or tertiary amines, such as pyridine or triethylamine.

Carboxylic and sulfonic acid halides of Formula III are obtained in the usual way, for example by treating toluene carboxylic acid halides or toluene sul-fonic acid halides, as for example 4-toluene carboxylic acid chloride, 3-toluene carboxylic acid bromide, 2-toluene carboxylic acid chloride or 4'-toluene sulfonic acid chloride, with chlorine or bromine or by chlormethylating toluene sulfonic or carboxylic acids and converting the resultant sulfonic or carboxylic acids into the corresponding acid chlorides. Toluene sulfonic or carboxylic acids can also be treated with chlorine or bromine and the reaction products converted into the sulfonic or carboxylic acid chlorides or bromides.

'I'he azo dyes of the general Formula II may bear the acylatable aminogroups in the coupling component or in the diazo component. Azo dyes which bear the amino group in the diazo component are obtained for example by coupling .diazotized 1-amino-4-acetylaminobenzene-3- sulfonic acid with 1-hydroxybenzene-4-sulfonic acid, 1- hydroxynaphthalene-4-sulfonic acid or Z-hydroxynaphthalene-S-sulfonic acid and splitting off the acetyl group from the azo dye formed in the usual way.

Azo dyes which contain the amino group in the coupling component are obtained for example by coupling diazotized aromatic amines with aniline or toluidine or 1-hydroxy-8-aminonaphthalene-3,6-disulfonic acid in an acid medium. 2

Suitable carboxylic and sulfonic acids include 4-chlormethylbenzoyl chloride, 3-chlormethybenzoyl chloride, 2- chlormethylbenzoyl chloride, 5 -bromomethylbenzoyl bromide, 3-bromomethylbenzoyl bromide, 4-chlormethylbenzene sulfonic acid chloride, 3-chlormethylbenzene sulf'onic acid chloride, 4-bromomethylbenzene sulfonic acid bromide and 3-bromomethyl benzene sulfonic acid bromide.

Another possibility for the production of the new dyes resides in the coupling of a diazotized amine of the general formula:

A-NH IV with a compound capable of coupling of the general formula:

in which A, B, X and Y have the meanings given above.

The coupling is carried out in the way usual for the production of azo dyes from diazotized amines and compounds capable of coupling, for example in aqueous medium and while cooling.

Compounds capable of coupling of the Formula V include 1 hydroxy-4 (4-chlormethylbenzoylamino)-napl1- thalene-3,6-disulfonic acid, 1-hydroxy-4-( 3 bromo-methylbenzoylamino)-naphthalene-3,5-disulfonic acid, 1-(3-(3- chlormethylbenzenesulfonylamino) phenyl) 3 methylpyrazolone-(S) and l-hydroxy-6-(2-chlormethylbenzoylamino)-naphthalene -3-sulfonic acid.

These compounds are obtained byreacting carboxylic acid halides or sulfonic acid halides of the 'Formula III with the corresponding compounds capable of coupling which contain amino groups, of the formula:

The reaction conditions. are the same as given above for the reaction of the halides of Formula III'with the azo' dyes of Formula II.

A third method for the production of the new azo dyes consists in coupling diazotized amines of the general formula: @i hitFA-NH;

OH2X VII with compounds capable of coupling of the general formula I-IB VIII acid-binding substances.

With the new azo dyes of the Formula I, the abovementioned textile materials, can be dyed in a long bath and also by padding or printing. Padding and printing are the preferred methods of dyeing. Furthermore, synthetic or semi-synthetic substances such as nylon 6, or nylon 66 may be dyed with'the new dyes of this invention by conventional spin dyeing methods.

Of the new dyes, those are especially preferred which contain one or more sulfonic acid groups in the molecule.

When dyeing with the new dyes, the procedure may for example be thatcotton is padded with an aqueous solution of the dye and, preferably after drying, led through a bath which contains a basic-reacting substance, such as sodium hydroxide, sodium carbonate, sodium, hydrogen carbonate, potassium hydroxide or potassium carbonate, possibly also neutral salts, such as sodium chloride and sodium sulfate. The dye is then fixed on the fiber by steaming for a short time. Instead of steaming,

I there may also be used a treatment with air at to 200 C., preferably at to C. The basic-reacting substance and possibly the neutral salts may however be added to the padding bath. Furthermore, cotton for example may be dyed from an aqueous bath with the dye with the addition of basic-reacting substances and neutral salts at 20 to 30 C., and the'dye fixed by gradually raising the bath temperature. Finally, cellulosic materials may be treated with aqueous solutions of basicreacting substances, then padded with a dye of the said kind and the dyeing then fixed.

In printing structures containing cellulose, the dyes, advantageously together with the usual thickening agents, such as sodium alginate or tragacanth, possibly together with a usual printing auxiliary, and basic-reacting substances of' the said kind, are applied; the material to be printed is dried and steamed for a short time. The dye.

may also be printed onto the structure together with thickening agents and conventional printing auxiliaries, thestructures dried, led through a bath charged with basicreacting substances, again dried and then steamed.

Dyeings and prints with very good wet fastness are.- obtained.

The following examples will further illustrate this in-- vention but the invention is not restricted to these examples. The partsv and percentages are units of weight. Where parts by volume are referred to, these bear the same relation to the parts by Weight as the liter does to the kilogram under normal conditions.

Example 1 20 to 22 parts of l-chlormethylbenZene-4-carboxylic acid chloride are added with vigorous stirring to a suspension of 31.9 parts of 1-amino-8-hydroxynaphthalene- 3,6-disulfonic acid and 250 parts by volume of water and the pH is kept at 4 to 5 by allowing a 50% aqueous solu tion of sodium acetate to flow into the mixture.

After about five hours stirring, the deposited precipitate is filtered off, washed with sodium chloride solution and dried. About 33 parts of the compound of the formula:

I SOaH HOsS zene carboxylic acid bromide.

Further coupling components are obtained by using 2- amino-S-hydroxynaphthalene-6-sulfonic acid, 2-amino-5- hydroxynaphthalene-7-sulfonic acid, Z-hydroxynaphthalene-3 carboxylic acid (3-arnino phenylamide), 1 (3- aminophenyl)-3-methylpyrazolone (5) or 1 (4 aminophenyl)-3-methylpyrazolone-(5) instead of l-arnino-8-hydroxynaphthalene-3,6-disu1fonic acid.

The coupling components of the above specified formula can be directly fixed on the fiber, for example by padding cotton fabric with an aqueous solution which contains in 1000 parts by volume 20 parts of the coupling component and 4.5 parts of sodium hydroxide, drying the fabric and then steaming it for 5 minutes at 100 C. or treating it with hot air at 140 C. for 5 minutes. The padded material is then rinsed and soaped. Thereafter it is padded with an aqueous solution which contains in 1000 parts by volume 5 parts of diazotized 1- aminobenzene-4-sulfonic acid. A violet dyeing is obtained with very good wet fastness properties.

dyelng.

Diazo component Coupling component Shade l-amino-Z-nitrobenzene 1-hydroxy-8(4- Bordeaux.

chlormethyl-benzoylamino) naphthalene-3,6-disulfonic acid. 1-amino-2-rnethoxy-benzene do Do. l-amino-Z-ethoxybenzene.- do Do. I-amindZ-methylbenzene do Do. 1-aminobenzenc2-sulionic acid do Red.

amide. l-aminobenzene li-sulfonic acid do Do. 1-aminobenzene-3-sulfonic acid do Do.

amide. 1-amino-4-nitrobenzene do V1o1 et. 1-amino-4-methy1benzene. do Bluish red l-amino-4 methoxybenzene do Violet. 1-amino-4-ethoxybenzenedo Do. 4-amino-azobenzene do Do. 4-amino-azobenzene-4 sulf0nie do Do.

acid. 1-aminobenzene-4sultonic aciddo ed. 1-amino-4-cblorbenzene do Reddish violet 1-amino-4-acetylaminc-benzene.- do Violet. l-amino-2-methoxy-Sehlorbenzene. l-aminobenzene-2,5-disulionie acid. 1-amino-2-methoxy-benzene-5- do Reddish sulfonic acid. violet 1-amino-2-methoxy-benzene-5- do D0.

suli'onic acid dicthylamide. l-ami1nouaphthalene-4-su1fonic do Violet.

801 l-aminonaphthalenedsulfonic do Do.

a l-amiinonaphthalene-7-sulionie do Do. aci 1-amino-4-benzeneazo naphthado Bluish ne. black l-amino-4-(4-suliobenzeneazo) do Do.

naphthalene. 1-amino-2,5-dimethoxy+benzodo Do.

ylalnino benzene. 1-amino-2,5-diethoxy-4-benzodo Do.

ylamino benzene.

Diazo component Coupling component 1-amino-4-ethoxybenzenc 4-am1noazobenzene 4 aminobenzene 4 sulionic acid amide 1-amino-4-chlorbe11 ene LaminoA-aoetylaminobcnzene l-amino-2-methoxy-5-ch1orbenzenc l-aminobenzene-Z,fi disulionie acid- 1 amino 2 methoxybenzene 5 sulionic acid.

1 amino 2 methoxybenzene 5 sulfonic acid diethylarnide.

1 aminonaphthalene 4 sulfonic acid 1 aminonaphthalene 6 sulfonic 1 aminonaphthalene 7 sullonlc 1 amino 4 benzencazo naphthalcne.

1 amino 4 (4 suliobenzcneazo) naphthalene.

1 amino 2,5 dimcthoxy 4 benzoylarninobenzene.

1 amino 2,5 diethoxy 4 benzoylaminobenzene.

l-amino-Qmitrobenzene acid. l-amino-2-methoxybenzene-5- sulionic acid. 1-amino-2-methoxybenzene-5- l-aminonaphthalene-G-sulionic 1-a1ninonaphthalene-7-sulfonie aei l-amino i benzeneazo naphtha- Lamino t-(4-sulfobenzeneazo) naphthalene.

1amino-2,5-dimethoxy-4-benzoyL amino benzene.

l-amino-2,5-diethoxy-4-benzoylamino benzene.

1-hydroxy-6(4-ehl0rmethylbenzoylamino) naphtha 1ene-3-sulfonic acid.

Do. Bluish red.

Violet.

dye by adding sodium chloride.

The deposited dye is filtered off by suction, washed with 10% sodium chloride solution and then dried. The dye thus obtained can be fixed on the fiber for example as follows: cotton fabric is padded with an aqueous solution which contains 20 parts of this dye in 1000 parts by' volume. fabric is squeezed to moisture content and dried.

Then the 8 Then it is led through a second padding bath which con tains 15 parts of sodium hydroxide and 200 parts of Coupling component Shade sodium chloride m 1000- parts by volume, squeezed, ISDteamed forhS minutes at 100 C. and s p the boill-hydlroxy-S-acetylaminonaphthalenc-ii,5-disulfonic Bluish red.

nc 8.01 ye s wit very good wet fastness are obtained. 5 i ig i g a w f acid 3 -p eny- -met y pyrazo one- 5 e W. Example 2 d-p1henyl-Zi-methyl-5-n;1inoyra%ole F".5733"..- go. -p euypyrazo one- -car 0x to aci ami e- 07 9.5 parts of 1-chlormethylbenzene-4-carboxylic ac1d 1 (2,541icmorphenyl) s methylgyrazolone (5) chloride are added to a mixture of 9.4 parts of 1,4-d1- i-( p y y py 0 D0. amiuobenzene-3-sulfonie acid and 100 parts by vol- 10 2E3$55$325355;ifififiigiiidiiifi i 1 38: time of water and while stirring powerfully saturated %-(figg pg yl)ggylpy g aqueous sodium acetate solution. is allowedto flow 1n :iifig gig igfii ifii ifi gfiiigigfiifi 3: in such an amount that a pH of to 5 is set up in the -(4-111tr0phcny1)-3-methy1pyrazo1one-(5) Do. mixture. After 4 to 5 hours, the -1 (4-chlormethylben- SOKH zoylamino)-4-aminobenzene-3-sulfonic acid obtained in the form of a grey precipitate is filtered off, dissolved in H0 Brown 200 parts of 2% hydrochloric acid and diazotized with a solution of 3.5 parts of sodium nitrite in 50 parts of 5 water. This diazo solution is added gradually to a solution of 16 parts of l-amino-8-hydroxynaphthalene-3,6- 20 g disulfomc ac1d in 200 parts of water, a pH of 6 to 7 being maintained by adding sodium carbonate solution. The dye formed is precipitated with excess sodium chlo- Example 3 ride and dried. It is obtainedin the form of a violet 7 v powder and dyes cotton violet shades of good wet fast- 23 parts of 1-acetylamino-4-aminobenzene-3-sulfonic ness from an alkaline bath. acid are diazotized in the usual way and the diazo solu- Dyes having similar properties are obtained by using, tion is coupled with 22.4 parts of l-hydroxynaphthaleneinstead of l-amino-S-hydroxynaphthalene-3,6-disulfonic 4V-sulfonic acid. By adding 50 parts of 35 hydrochloric acid, the coupling components specified in the following acid and excess sodium chloride, the dye formed is pretable. The shade given in the right-hand column relates cipitated and, after filtration, is stirred in the form of an to the finished dye. aqueous paste together with 1000 parts by volume of a 10% aqueous sodium hydroxide solution for an hour at Coupling component: Shade 90 to 100 C. Then such an amount of hydrochloric. acid is added to the mixture that a pH of about 4 is setlNigIlibig-(Zxyfgxyeflisfll)gninobeilgeue ufiib geddish volet. up and the deposited precipitateiis filtered oif. It is made -t isy roxye y amino- -me y enzeue cc. l-lNtN-bis-(2-hydroxyethyl) amino]-3-chlorbenzenc Eeddish violet. mto an aqueous Paste Wlth 500 m by Volume of y -Q- s' Y Y naphthalene Y 101%. ter; to this paste there are added with powerful StirIlng N-methyl-N-(2-hydroxyethyl) ammobeuzene" Red. 1 2-hydroxynaphthalene D0. 20 to 25 parts of 1-chlormethyloenzene-4-carboxyhe ac1d 2-hydroxyuaphthalene-B-sullonic acid D0. 241W!0Xmaphthalene s sulfonic Midum In 40 chloride, such an amount of saturated aqueous SOdllllTl 2-hydroxynaphthalene3,fi-disull'oriic acid Do. acetate solution being allowed to flow in that a-pH of figf ggfggf gg ac1d (Zhydfmy 4 to 5 is set up' in the mixture. After 4 to 5 hours, the. fyg g y phghalgne-a-earbqxyli a i tfi duilidegau B1 Dho. d dye formed is precipitated with excess sodium chloride, g fi g fj g j enzoy ammonap a ms m filtered, washed with dilute sodium chloride solution and 1 (iishgfgl'ntgggcgd acetylaminonaphthalene 3,6 Do. dried. parts of a red powder are obtained which 14 g:ox -eammona hthale i a siflrome eid orai e. dyes cotton clear red shades of excellent wet fastness. l-hy roxy-fi-acetylaminonap t aene-3-s onic act 0. l-hydroxy-Tamin0naphtl1alene3-suli0nic acid Red. Dyes of Smnlar properties {maimed m the Same i-gygoxynaplfizlfialenel {fii 130. way from the azo dyes prepared in analogous manner OX 9. a enc -S 01116801 0. l-hgdroxgaghthalene-s,8-disulIonic acid Do. and the acylatmg agents 111 the followmg table- Example Azo dyestufi Acylating agent Shade 4 I 0100 Red.

S 03H i I CHzCl V SO H OH SOZH I 5 OlOO CHzCl D0.

I OH SOaH 6 C1802 OH2Cl Orange.

We claim: 5. The azo dye of the formula XHaO S0311 HO\N/N SOaH wherein: I

X is a member selected from the class consisting of chlorine and bromine, m is an integer of from to 2, inclusive, and B is a coupling component selected from the class consisting of the naphthalene, phenylazo-naphthalene and l-phenyl-pyrazalone-(S) radicals in which the The azo dye of the formula substituents are limited to members selected from the class consisting of hydrogen, hydroxy, methyl, 15

chlorine, nitro, carbamyl, amino, acetylamino, ben- Q H zoylamino, hydroxyethylamino, hydroxyethylamino- I N carbonyl and phenylaminocarbonyl. 2. The azo dye of the formula I H 7 O1 C1CHz-O ONHN=N 110 s S OaH I I References Cited in the file of this patent S0311 UNITED STATES PATENTS The azo y of the formula 2,254,602 Fleischhauer et a1. Sept. 2, 1941 OH 2,931,795 Heckendorn et al. -9 Apr. 5, 1960 SO H 11038 4. The azo dye of the formula OH T C1GH2C o-NH-rN=N l SOzH SOaH- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,117,962 January 14, 1964 Werner Rohland et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 6, in the table, first column, line 65 thereof, after "-5-" insert sulfonic acid diethylamide columns 9 and 10, in the table, second column, third formula thereof, lower left-hand portion thereof, strike out "HO S-"; same tab 1e, second column, sixth formula thereof should appear as shown below instead of as in the patent:

N --OH SO H Signed and sealed this 11th day of August 1964.

(SEAL) Attest:

ERNESTW. SWIIJER v EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. AN AZO DYE OF THE FORMULA 